Sustainably electrified co-production of Nylon-6 and Nylon-66 monomers via divergent paired-electrolysis with matched electron stoichiometry

Cyclohexanone oxime (CHO) and adipic acid (AA) are essential monomers in the production of Nylon-6 and Nylon-66, respectively, yet their conventional syntheses are typically energy-intensive and environmentally unfriendly. Herein, we report a novel divergent paired-electrolysis strategy for the sustainably electrified co-production of CHO and AA in a two-chamber cell under ambient conditions, using cyclohexanone (CYC) as the sole feedstock. By elaborately exploring the optimized electrocatalysts, we achieved thermodynamically and kinetically favorable cathodic nitrate (NO 3 − ) reduction reaction (NitRR) and anodic CYC oxidation reaction (CycOR), outperforming the competing hydrogen evolution reaction and oxygen evolution reaction. This unique approach enables high-yield and selective concurrent production of CHO and AA at low cell voltages. Specifically, the cathodic bismuthene (Bi-ene) catalyst selectively produces NH 2 OH with a remarkable FE of 86.27% and a yield rate of 214.79 μmol h −1 cm −2 at a stable current density of ~57 mA cm −2 , as the exergonic release of adsorbed NH 2 OH avoids over-reduction to NH 3 , which then facilities the CYC oximation, achieving 97.98% CHO yield. Meanwhile, the in-situ formed electrophilic oxygen species (Ni 3+ –OOH) from nickel hydroxide promotes the CycOR at the anode, yielding AA with 91.96% FE and 92.98% selectivity. Notably, the divergent paired electrolysis system maintains excellent performance over 120 hours of continuous electrolysis. This synergistic paired-electrolysis system delivers compatible current densities at both electrodes owing to the well-matched electron stoichiometry, establishing an exceptionally efficient system for the simultaneous electrosynthesis of dual Nylon monomers. This work demonstrates an efficient and scalable electrosynthesis platform for valuable chemical production, presenting an inherently sustainable paradigm for renewable electricity-driven chemical manufacturing. Divergent paired-electrolysis enables sustainable co-production of cyclohexanone oxime (97.98% yield) and adipic acid (91.96% Faradaic efficiency) from cyclohexanone as the sole precursor, via synergistic cathodic nitrate reduction and anodic cyclohexanone oxidation under ambient conditions. • Simultaneous electrosynthesis of Nylon-6 and Nylon-66 monomers. • High yield and selectivity of cyclohexanone oxime and adipic acid are achieved. • Operando EIS and DFT clearly reveal the reaction mechanisms.